Preferentially modified stereoregular polyhydrocarbons



United States Patent 3,505,429 PREFERENTIALLY MODIFIED STEREOREGULAR POLYHYDROCARBONS Jack J. Press, Teaneck, NJ. (5788 Eldergardens St., San Diego, Calif. 92120) No Drawing. Continuation-in-part of application Ser. No. 427,518, Jan. 22, 1965, which is a continuation-in-part of application Ser. No. 113,972, Apr. 4, 1961. This application Oct. 22, 1965, Ser. No. 502,720

Int. Cl. C08f 29/12 U.S. Cl. 260857 7 Claims ABSTRACT OF THE DISCLOSURE A stereoregular polyhydrocarbon composition in which a synergistic modifier combination for conferring dyeability is preferentially incorporated in the amorphous regions.

The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

This application is a continuation-in-part of my copending applications Ser. No. 427,518, filed Jan. 22, 1965, now abandoned, and Ser. No. 113,972, filed Apr. 4, 1961, now abandoned and titled A Process of Preferentially Modifying stereoregular Polyhydrocarbons.

The invention relates to stereoregular polyhydrocarbons. More particularly, this invention relates to polymeric compositions having improved affinity for dyes, said compositions containing a major amount of stereoregular polyhydrocarbons.

It is known that polyethylene is vastly unsuitable for the production of textile fibers due to the relatively poor properties imparted to the product. For one thing, staple polyethylene fiber will not hold a crimp and this is necessary for textile processing. For another, it is useless to make a textured or stretch yarn from continuous filament polyethylene yarn because the characteristics imparted to the yarn are not maintained during weaving, dyeing, or ordinary use. Further, the material from which a fabric is made must be thermally stable before it may be subjected to ordinary use. It must not have a relatively low melting point, and the final fabric must not have a high degree of heat sensitivity, nor relatively soft mechanical properties at elevated temperatures. However, the thermal properties of a polyethylene fabric are such that it is impossible to subject it to ordinary ironing without physically damaging the fabric and it has been found to shrink in the conventional dryer. As is apparent from the foregoing, polyethylene cannot be utilized in the manufacture of everyday fabrics for ordinary use.

In recent times, it has been found that certain linear crystalline hydrocarbon polymers containing stereoregular macromolecules and having melting points between 150 and 300 C. can be used for the production of textile fibers without the inherent difficulties encountered with the use of polyethylene polymers for this purpose. Aside from melting point diiferences, polypropylene with a tertiary carbon and a methyl side chain, crystallizes differently and has a much higher resilience and elasticity. These properties are essential in generally useful textile fiber. Further, polymers of olefinic hydrocarbons containing stereoregular macromolecules, such as polypropylene, polystyrene, polymethylpentene, poly 4 methyl l-hexene, offer considerable advantages in the production of fibers, particularly because of their good mechanical properties and light weight. However, such polymers have not been satisfactory because of their poor aflinity for dyes,

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this poor afiinity being due to the particular chemical nature of such polyolefinic hydrocarbons.

Many processes have been proposed in order to improve the affinity of such polyhydrocarbons for dyes, such as the addition of soluble solid substances to the molten polyolefin before spinning. The addition of basic substances facilitates dyeing with acid dyes, whereas the addition of acid substances favors dyeing with basic dyes. However, such processes have not been completely satisfactory because soluble modifiers interfere with crystallization, impair strength and thermal stability, and are not sufliciently available in the amorphous regions where dyeing takes place.

It has also been proposed to increase the aflinity of dyes for polyhydrocarbon type fibers by grafting monomers onto the fibers after subjecting the fibers to a preliminary peroxidation or to high energy radiation. When such processes are applied to the polyolefin after it is in filamentary form the surface properties of the grafted fibers are considerably modified and the dye receptivity is improved. However, when such processes are applied to highly crystalline filaments, any grafting onto the preformed fibers takes place only at the surface. Therefore, subsequent dyeing is limited to the surface portion of the fiber and the dye does not penetrate inside the fiber.

In my co-pending application, Ser. No. 406, 631, filing dates Oct. 26, 1964, now U.S. Patent 3,337,652 I teach that the aflinity of polyolefins for dyes may be enhanced through the use of selected polymers in combination with specified low molecular weight fatty secondary modifiers. The latter modifiers, which have negligible dyeability by themselves, have molecular weights up to 5000. They associate themselves with the primary polymeric modifiers in such a way as to give synergistic combinations that are fusible at temperatures not exceeding the temperature of processing of the polyolefin.

For optimum efficiency, however, the primary and secondary modifiers must be chosen and processed so that they will interact uniformly and efliciently, when dispersed in the polyolefin, to give a complex with improved synergistic utility. In actual practice, it is somewhat difficult to achieve and maintain optimum complex formation before and during melt mixing with the polyolefin. In addition, the fatty, low molecular weight secondary additives which have not complexed with the hydrophillic polymer may sweat out of the polyhydrocarbon and interfere with processing or it may excessively plasticize the primary polymer and cause sticking during processing.

In another copending application, Ser. No. 427,518 filed Jan. 22, 1965, now abandoned, I teach that the affinity of polyhydrocarbons for dyes may be further improved, over and above the improvement achieved with polymeric materials alone, and comparable with that achieved with the above synergistic combination. This may be accomplished by replacing the above secondary additives of the synergistic combination with one of a specified number of higher molecular weight or higher melting secondary polymeric additives. In this way, the difficulties encountered with the use of the low molecular weight or low melting secondary additives are eliminated while the improvement achieved is maintained. As an added advantage, high speed commercial processing rates can be increased and there is some improvement in fiber stiffness.

I now have discovered that with the same synergistic combinations as disclosed in applicaiton Ser. No. 427,518, I can obtain further desirable improvement in dyeability at the lower levels of modification and with lower percentage levels of secondary modifier. With modifier levels of 1 to 20%, preferably 1 to 10%, the proportion of primary modifier can be raised to to 99% and the secondary modifier can be reduced to 1 to 5% of the total modifier. Even at lower percentages of primary and higher percentage of secondary as described in United States Patent 3,425,060, further improvements in dyeability are achieved through preferential modification by concentration in the amorphous regions as shown in Example 5 hereinafter described. This appears to result from improved dispersion of the modifier, preferentially in the amorphous regions, and more uniform interaction of the primary and secondary modifiers. This latter development is described in my copending application titled A Process of Preferentially Modifying Stereoregular Polyhydrocarbons. Reduction in modifier level with good dyeability and improved processability is most desired to reduce cost, adverse eifects on fiber properties and color.

It is therefore an object of this invention to provide polymeric compositions containing synergistic combinations, said compositions have improved afiinity for dyes devoid of the major difiiculties of the prior art.

Included in this invention are stereoregular structures with increased aifinities for dyes comprising a matrix of a stereoregular predominate isotactic and/ or syndrotactic polyhydrocarbon taken from the group consisting of:

(a) polypropylene,

(b) polymethylpentene, (c) polymethylbutene,

(d) polystyrene, and

(e) poly-4-methyl-1-hexene said matrix having concentrated in the amorphous regions thereof between 1 and of a synergistic combination consisting of:

(1) 95 to 99% by Weight of a modifying polymer which is hydrophilic, non-soluble in the polyolefin, said modifying polymer containing at least 25% of an oxygen containing N-alkenyl heterocyclic monomer and being selected from the group consisting of:

(a) poly N-vinyl oxazolidinone (b) poly N-vinyl methyl oxazolidinone (c) poly N-vinyl pyrrolidone,

(d) poly N-vinyl methyl pyrrolidone,

(e) poly N-vinyl oxazolidone,

(f) poly N-vinyl morpholinone,

(g) poly N-isoprenyl pyrrolidone,

(h) poly N-acrylyl pyrrolidone,

(i) a copolymer of 30% N-vinyl pyrrolidone and 70% vinyl acetate,

(j) a copolymer of 70% N-vinyl pyrrolidone and 30% vinyl acetate,

(1:), a copolymer of 80% N-vinyl pyrrolidone and 20% styrene,

(l) -a copolymer of 70% N-vinyl pyrrolidone and 30% ethyl acrylate,

(m) a copolymer of 70% N-isoprenyl pyrrolidone and 30% ethylene oxide,

(n) a copolymer of 60% N-acrylyl pyrrolidone and 40% ethyl acrylamide,

(o) a copolymer of 60% N-vinyl oxazolidone and 40% acrylonitrile,

(p) a copolymer of 50% N-vinyl methyloxazolidone and 50% vinyl acetate,

(q) a copolymer of 50% N-vinyl morpholinone and 50% methyl methacrylate,

(r) a copolymer of 90% N-vinyl pyrrolidone and 10% ethylene,

(s) poly N-vinyl morpholine, and

(2) 1 to 5% by weight of a material selected from the group consisting of: (a) polyvinyl alkyl ethers, (b) polyvinyl esters, (c) polyvinyl acids, ((1) a copolymer of an ethylenieally unsaturated acid with styrene,

(e) a copolymer of an ethylenically unsaturated acid with ethylene,

(f) polyvinyl alcohol,

(g) epoxy polymers,

(h) polyesters,

(i) polyamides, and

(j) polyamines,

said synergistic combination being fusible with said polyolefin at temperatures up to 350 C.

The stereoregular polyolefins which may be used within the concept of this invention include isotactic and syndiotactic polyhydrocarbons. These materials are usually made by utilizing stereo-specific catalysts which give polymers which are substantially linear and which develop a high degree of crystallinity.

A preferred class of my primary polymeric modifiers consists of polymers derived from oxygen containing N- alkenyl heterocyclic monomers, particularly alkenyl substituted lactams, oxazolidone, oxazolidinone, morpholine and morpholinone monomers. This includes copolymeric material containing at least 25% and preferably 50% of an oxygen containing N-al-kenyl heterocyclic monomer and an ethylenically unsaturated hydrocarbon, ester, ether, epoxide, amide or nitrile comonomer. This class of polymers is highly desirable because it has little or no basicity and has very high levels of affinity for a wide range of dyes. My preferred primary modifiers are neutral or only very slightly basic and yet in polyolefins, surprisingly, have higher dyeability with anionic (acid) dyes than the much more basic polymeric modifiers. In these monomers and polymers, the alkenyl substituted nitrogen is part of an internal amide group and is essentially neutral. Addi tional ring and substitued oxygen containing groups are more acidic than the substituted amide nitrogen and further reduce basic.

The secondary additives which may be used with the primary polymeric modifier to give synergistic combinations include the following:

(1) Polyvinyl alkylethers such as:

(a) polyvinyl ethylether, '(b) polyvinyl methylether, and (c) poly (vinyl methyl ether/maleic anhydride).

(2) Polyvinyl esters such as:

(a) polyvinyl acetate,

(b) polymethyl methacrylate, (c) polybutyl methacrylate, and (d) polyethyl acrylate.

(3) Poly acids such as:

(a) polyacrylic acid,

(b) polymethacrylic acid,

(0) sulphonated polyvinyl toluene,

(d) poly (ethylene/ sodium styrene sulphonate), (e) poly (styrene/maleic acid) partial esters, and (f) poly (ethylene/maleic acid).

(4) Polyhydroxy compounds such as:

(a) polyvinyl alcohol,

(b) partially hydrolyzed polyvinyl acetate with 20 to 70% residual acetyl groups, and

(c) hydroxyethyl cellulose.

(5) Epoxy polymers such as:

(a) bisphenol A-epichlorohydrin polymers with no reactive epoxy groups, and (b) bisphenol A-epichlorohydrin polymers with reactlve epoxy groups.

(6) Polyester condensation resins such as:

(a) adipic acid-propylene glycol, (b) isophthalic acid-ethylene glycol, (c) fumaric acid-propylene glycol bisphenol A, and, (d) terpene-tnaleic anhydride.

(7) Polyamide resins such as:

(a) dimerized linoleic acid-alkylene diamines,

(b) polycaprolactam nylon, and

(c) sebacic acid hexamethylene diamine/caprolactam terpolymer.

(8) Polyamine resins such as:

(a) dimerized linoleic acid-poly (alkylenc amine) resins with free amino groups,

(b) polymethyl ethyleneimine,

(c) polydimethylaminoethyl methacrylate,

(d) poly N-vinyl carbazola, and

(e) poly N-butyl vinyl quinoline.

The following examples set forth typical synergistic combinations of primary and secondary modifiers falling within the concept of this invention. Each is followed by results quite clearly illustrating the synergism encountered and the improved results obtained at low modifier levels with more uniform dispersion and interaction in the amorphous regions of the polyhydrocarbon.

EXAMPLE 1 Ninety-seven parts by weight of finely powdered (50 to 200 mesh) isotactic poly-4-methyl-1-pentene (M.P. about 235 C., isotacticity about 90%) was intimately mixed with 2.9 parts of finely powdered (50 to 200 mesh) poly-N-vinylmethyloxazolidinone (M.W. about 150,000) and 0.1 part of polyvinyl methyl ether (M.W. 10,000).

The mixture was then divided into two lots, A and B. The two lots were then compounded, under different process conditions, using a conventional screw extruder, water bath and pelletizer. The extruder had a one inch polyethylene type screw with a 24:1 L/D' (length/diameter) ratio, five compensating temperature controlled barrel heat zones, an adjustable gate valve for back pressures up to 10,000 p.s.i., and a heated four strand die. Lot A was compounded under normal conditions at zone temperatures of 250 to 300 C., a back pressure of 400 p.s.i. and a die temperature of 300 C. Lot B was preferentially compounded at temperatures below the crystalline melting temperature at temperatures for zones one to four of 150 to 200 C., a fifth zone temperature of 245 C.,

a back pressure of 10,000 p.s.i., and a die temperature of 265 C. Process time at temperatures below the crystalline melting temperature was greater than one minute. The pellets were oven dried to remove water.

The pellets were then converted to multifilament yarn under normal processing conditions using a similar 20:1 L/D extruder in combination with a variable speed metering pump, a heated die zone, a 34 hole (0.025 dia.) die, an air quench chamber and a variable speed tube take-up winder. The as-spun yarn was then hot drawn 300% to give the final yarn.

Lots A and B were processed into yarn to evaluate comparative process efficiency and subjective fiber characteristics. Process efficiency was compared at a normal constant (20 r.p.m.) pump speed by determining the finest final fiber size (denier per filamentd.p.f.) that could be made with no filament breakage in one hour and by determining the highest one hour as-spun production rate (500 to 2000 feet per minutef.p.m.) for final 165 denier/34 filament yarn with increasing, constant ratio pump and take-up speeds.

Lot A could not be processed at the normal pump speed without filament breakage for fiber up to 20 d.p.f. in the one hour test, and, could not be made into 165/ 34 yarn at the lowest take-up speed. The filaments coming from the die were uneven along their length and did not draw down uniformly in spinning. Lot B processed satisfactorily down to 3 d.p.f. and at a production rate for 165/34 yarn of over 1000 f.p.m.

The lot B yarn was made into skeins, scoured and dyed at a 40/1 bath to yarn ratio for one hour at the boil, separately, with Colour IndexDisperse Blue 27 and 6 Colour IndexAcid Red 127. The dyes were used at a one percent, O.W.F. (on weight of fabric) concentration. The yarn samples were dyed uniformly to a medium shade of blue with the disperse dye and to a light red shade with the acid'dye. Both dyeings withstood repeated laundering with negligible color loss.

Comparable results were obtained with isotactic polystyrene instead of poly-4-methyl-1-pentene for similar modification and processing.

EXAMPLE 2 In accordance with the procedure of Example 1, I prepared and evaluated modifications of a representative stereoregular polypropylene (M.P. 170 C., M.W. about 350,- 000, melt index 3 and isotacticity of The modified polyhydrocarbon contained 4% by weight of primary modifier poly-N-vinyl pyrrolidone (M.W. 40,000) and 0.2% of a polyester condensate of adipic acid and propylene glycol (M.W. 12,000). Lots A and B were modified, pelletized and spun in.o yarn, as in Example 1, except that the normal compounding conditions (A) were 200 to 250 C. Zone temperatures, 350 p.s.i. back pressure, and 250 C. die temperature; and the preferential compounding conditioning (B) were to 170 C. zone temperatures, 8000 p.s.i. back pressure, and 200 C. die temperature.

Lot A modified polymer when spun could not be processed at normal pump speed for an hour without excessive filament breakage, and, could not be made into 34 yarn at the lowest take-up speed used. The filaments were uneven and did not draw down uniformly. Lot B processed satisfactorily down to 3 d.p.f. and at a production rate for 165/34 yarn of over 1000 f.p.m.

The Lot B yarn dyed well with the blue disperse dye and the red acid dye and showed negligible loss in color with repeated launderings.

Comparable results were obtained when using is'otactic poly-4-methyl-1-hexene instead of the isotactic polypropylene.

EXAMPLE 3 In accordance with the the procedure of Example 1 and the processing conditions of Example 2B, I modified and evaluated a higher melt index polypropylene (M.P. C., melt index 15, isotacticity 99% Modification 3A was made with 10% by weight of primary modifier, a 50/50% by weight copolymer of N- vinyl-methyloxazolidinone and vinyl acetate, together with 0.1% by weight of a polycondensate of dimerized limoleic acid and triethylene tetramine (M.W. 6000, amine value of 90). Modification 3B was made with 10% by weight of primary modifier, a 70/30% by weight copolymer of N-vinyl-pyrrolidone and ethyl acrylate, together with 0.2% by weight of polymethyl methacrylate (low viscosity).

Both the 3A and 3B modified polypropylenes processed satisfactorily down to 2 d.p.f. and at a production rate for 165/34 yarn of 2000 f.p.m. Both yarns dyed readily to medium shades with the blue disperse and the red acid dyes. With higher dye concentrations (4% O.W.F.) both fibers dyed to dark blue and red shades and showed negligible loss in color with repeated laundering.

EXAMPLE 4 In accordance with the procedure of Example 1 and the processing conditions of Example 2B, I modified the polypropylene set forth on Example 2 with a series of primary polymeric modifiers at a 5% by weight level together with representative secondary polymeric modifiers at an 0.2% by weight level of addition.

The primary polymeric materials utilized included the following:

(1a) poly N-vinyl oxazolidinone (1d) poly N-vinyl methyl pyrrolidone (1e) a copolymer of 70% N-vinyl pyrrolidone and 30% N-vinyl lauryl pyrrolidone (11') poly N-vinyl morpholinone (1 g) poly N-isoprenyl pyrrolidone (1h) poly N-vinyl morpholine (li) a copolymer of 30% N-vinyl pyrrolidone and 70% vinyl acetate,

(1k) a copolymer of 80% N-vinyl pyrrolidone and 20% styrene,

(11) a copolymer of 70% N-vinyl pyrrolidone and 30% ethyl acrylate,

(1m) a copolymer of 70% N-isopenyl pyrrolidone and 30% ethylene oxide,

(1n) a copolymer of 60% N-acrylyl pyrrolidone and 40% ethyl acrylamide,

(lo) a copolymer of 60% 1 -vinyl oxazolidone and 40% acrylonitrile,

(lq) a copolymer of 50% N-vinyl morpholinone and 50% methyl methacrylate,

(Ir) a copolymer of 90% N-vinyl pyrrolidone and 10% ethylene,

The secondary additives utilized in making the disc included the following:

Polypropylene modified by the primary-secondary modifier combinations above were spun and evaluated for draw down and production rate potential. The results of such tests are shown in the following table. All of the yarns dyed light to medium shades with the blue disperse and red acid test dyes.

Modifier Draw Take-up down, rate, Primary Secondary d .p .i. f.p.m.

cecewwwmcomwwmwww All the variations were considered to have given satisfactory results in these preliminary production tests.

EXAMPLE In accordance with the procedure and processing conditions of Example 2, I prepared and evaluated normal and preferential modifications of the same polypropylene using representative primary modifiers in combination with higher secondary modifier percentages. Modifications A and B were made with 3.3 percent by weight of poly- N-vinyl-rnethyloxazolidinone and 0.7 percent of polyvinyl methyl ether. Modifications C and D were made with 1.5 percent poly-N-vinyl pyrrolidone and 0.15 percent of a polyester condensate of adipic acid and propylene g y ol. Modifications E and F were made with 4.5

percent of a 50/50 copolymer of N-vinyl-methyloxazolidinone and vinyl acetate with 0.5 percent of a polycondensate of dimerized linoleic acid and triethylene tetramine. Modifications G and H were made with 4.5 percent of a 70/30 copolymer of N-vinyl pyrrolidone and ethyl acrylate with 0.5 percent of a partially (40%) hydrolysed polyvinyl acetate.

The following results were obtained when the modifications were evaluated by the fine denier (d.p.f.) spin test, the 165/34 yarn production rate (f.p.m.) test, and the 1% O.W.F. dyeing tests with the disperse blue and the acid red dyes when the normal and preferential 165/34 yarns for each modification were dyed together, competitively, in the same dye bath.

-D Sha d depth Blue l 111 v1 n1 1 m 1 In Red V1 in tint l l m l 111 Even at higher ratios of secondary to primary modifier, preferential modification further improves the rate and extent of dyeability.

The modifiers, heretofore described, would be mixed with the stereoregular polyhydrocarbon at a temperature between the first and second order transition temperature of the polyhydrocarbon and at a pressure of to 20,000 pounds per square inch, as described in my copending application, Ser. No. 502,719, filing date Oct. 22, 1965, titled A Process of Preferentially Modifying Stereoregular Polyhydrocarbons, now US. Patent 3,425,969.

This is necessary in order to achieve the results taught, i.e., to concentrate the modifiers in the amorphous (noncrystalline) regions of the polyhydrocarbon where dyeing occurs. Due to the fact that the modifiers are so concentrated, smaller amounts of modifiers are necessary to achieve greater results in dyeability. This is indeed a great economic advantage to the industry.

The modifiers may be preferentially mixed during any stage of processing or blending of the polymer prior to use in the extrusion of fiber, film, coating or plastic. It may also be added as a liquid or powder to finely ground or micronized polyolefin polymers and then disposed in situ during hot dip or spray coating or during spreading and heat coating operation. They may be incorporated in polyhydrocarbon solutions or emulsions and then applied to surfaces with or without heating.

In my copending application, I show the use of selected hydroph ilic polymers to improve the dyebility of the stere regular, high melting polyolefin. The level of addition of these primary modifiers should be between 1 and 20% of the weight of the overall composition including polyolefin. As shown and substantiated herein by the results which follow each of the examples, the utility of these primary modifiers may be vastly improved by replacing from 1 to 20%, preferably not more than 5%, of the primary modifier by a secondary modifier, heretofore listed, which has limited utility by itself.

The synergistic effect of the combination, as taught, on the polyolefin includes vastly improved dyeability. However, the listed secondary modifiers also enhance the compatibility of the primary polymeric modifier in the polyolefin. These advantages are also accompanied by improvements in the processing of the overall combination and, surprisingly, many infusible primary modifiers are rendered fusible and may be utilized within the concept of this invention to improve the dyeability of a polyolefin structure as heretofore taught.

The level of addition of the polyolefin of the synergistic combination heretofore described should be between 1 and 20% of the weight of the overall composition. If less than 1% is utilized, significant improvement will not be achieved in dyeability. If an amount greater than 20% is added to the polyolefin, many of the physical properties of the final product will be adversely affected. These include loss of strength and a lower resistance to repeated flexing.

As the synergistic combination, it is desirable to use a minimum amount of secondary additive to minimize any adverse effects on the properties of the fibers. An addition of the secondary additive above the limit stated (20%) may be in excess of that required to associate and complex with the primary modifier which preferably makes up 95 to 99% by weight of the synergistic combination.

I prefer however to use not more than by weight of the secondary polar additive, since even between 5 and 20% there might be excessive reduction in the melting point of the combination and this would result in difficulties in processing, particularly drawing and drying.

It is also preferred that the addition of the secondary additive not go below 1% by weight because below this level very little improvement is achieved in dyeability.

The preferred primary polymeric modifier of the combination should comprise at least 25% by weight of an oxygen containing N-heterocyclic monomeric unit in combination with not more than 75% of an ethylenically unsaturated monomeric unit having no basic groups. If the latter unit is present in an amount over 75%, you obtain very low levels of dyeability. It is therefore necessary to use very excessive amounts of modifier to achieve desired results.

If the ethylenically unsaturated unit is present between 50 to 75% by weight, higher levels of addition are required. The melting point of the overall composition may be reduced to such an extent that the modifier, particularly at higher levels of addition, may give some problems in processing.

However, if the latter monomeric units are present below 50% by weight of the overall primary modifier, lower levels of addition can be used to improve dyeability without processing problems resulting from an excessive reduction in melting point. This represents the optimum from a commercial point of view.

Under present concept, I prefer hydrophillic polymeric primary modifiers as part of my synergistic combination which may be soluble in either water and/ or an oxygenated solvent but which are not soluble in the polyolefin. I do prefer modifiers which are fusible and can be dispersed in the polyolefin.

Prior experience with comparatively less hydrophobic fiber forming polymers, such as polyacrylonitrile polymers and polyamides, have shown that the use of hydrophillic, water soluble or dispersible, modifiers is impractical. Mainly because excessive amounts of the modifier are leached out in securing and dyeing processes. Surprisingly, I have found that my hydrophilic polymeric modifiers, when melt dispersed in the more hydrophobic polyolefin, have good dispersion stability and are not susceptible to leachage.

I have found that at comparatively low levels of addition, my synergistic combination, as taught, confers good dyeability on the polyolefin without the necessity for costly and sometimes impractical post treatments.

My hydrophilic primary polymeric modifiers must be fusible with the polyolefin. This is necessary for the formation of a continuous network of modifier throughout the polyolefin in order to permit dye peneration and efficient coordination of the dye and modifier throughout the film or fiber.

The use of a non-fusible, cross-linked modifier, which results in poor dispersion, is ineffectual. The required modifier network in such a case cannot be formed and the discrete, separate particles are surrounded by unmodified areas within the polyolefin matrix. As a result, dyeing is limited to the fiber surface and the dye cannot penetrate into the interior of the fiber where it is most desired.

It is generally recognized that dyeing takes place almost entirely in the more open and readily accessible amorphous areas. When a soluble modifier is utilized, it is usually spread throughout the amorphous and crystalline areas of the polyolefin. As a result, the modifier in the crystalline areas is not available for improvement in dyeability. It also interferes with crystallization and adversely affects strength and thermal stability. However, my synergistic combination is not sufiiciently compatible to be a part of the more uniform and denser crystalline areas. It appears to concentrate in the more amorphous areas where it is necessary for dyeability. It has also been found that an increase in molecular weight of my modifiers, further reduces compatability with stereoregular polyolefins and promotes concentration of the modifier in the more amorphous regions where it may improve the dyeability of the polyolefinic matrix.

Obviously, many modifications and variations of the present invention are possible in the light of the above teaching. For instance, the synergistic'combination of this invention may be used to increase opacity and the affinity of the polyolefin for finishes. They may also be used to improve the printability of the polyolefin, increase the adhesion of the polyolefin to other materials, or to reduce the overall static propensity of the final product. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

I claim:

1. A polymeric composition having improved affinity for dyes comprising:

a matrix of stereoregular polyhydrocarbon taken from the group consisting of polypropylene, polymethylpentene, polystyrene, poly-4-methyl-1-hexene, and polymethylbutene; said matrix having dispersed in the amorphous areas of said polyhydrocarbon, between 1 and 20 percent by weight of a synergistic combination consisting of:

(1) 95 to 99% by weight of a modifying polymer which is hydrophilic, and non-soluble in the polyolefin, said modifying polymer selected from the group consisting of:

(a) poly N-vinyl oxazolidinone (b) poly N-vinyl methyl oxazolidinone (c) poly N-vinyl pyrrolidone (d) poly N-vinyl methyl pyrrolidone (e) poly N-vinyl oxazolidone (f) poly N-vinyl morpholinone (g) poly N-isoprenyl pyrrolidone (h) poly N-acrylyl pyrrolidone (i) 30% N-vinyl pyrrolidone/70% acetate copolymer (j) 25 to 70% N-vinyl pyrrolidone/ to 30% vinyl acetate copolymer (k) N-vinyl pyrrolidone/20% styrene copolymer (1) 70% N-vinyl pyrrolidone/ 30% acrylate copolymer (m) 70% N-iSoprenyl pyrolidone/ 30% eth lene oxide copolymer (n) 60% N-acrylyl pyrrolidone/40% ethyl acrylamide copolymer (0) 60% N-vinyl oxazolidone/ 40% acrylonitrile copolymer (p) 50% N-vinyl methyloxazolidinone/50% vinyl acetate copolymer (q) 50% N-vinyl morpholinone/50% methylmethacrylate copolymer (r) N-vinyl pyrrolidone/ 10% ethylene copolymer,

said percent being by weight, and

(2) 1 to 5% by weight of a secondary additive having a molecular weight between 5000 and 500,000, said additive selected from the group consisting of:

(a) polyvinyl alkylethers selected from the vinyl ethylgroup consisting of: polyvinyl ethylether, polyvinyl methylether, and poly(vinyl methyl ether/maleic anhydride),

(b) polyvinyl esters selected from the group consisting of: polyvinyl acetate, polymethyl methacrylate, polybutyl methacrylate, and polyethyl acrylate,

(c) poly acids selected from the group consisting of: polyacrylic acid, polymethacrylic acid, sulphonated polyvinyl toluene, poly- (ethylene/sodium styrene sulphonate), poly(styrene/maleic acid) partial esters, and poly(ethylene/maleic acid),

(d) polyhydroxy compounds selected from the group consisting of: polyvinyl alcohol, partially hydrolyzed polyvinyl acetate with 20 to 70% residual acetyl groups, and hydroxyethyl cellulose,

(e) epoxy polymers selected from the group consisting of: bisphenol A-epichlorohydrin polymers with no reactive epoxy groups, and bisphenol A-epichlorohydrin polymers with reactive epoxy groups,

(f) polyester condensation resins selected from the group consisting of: adipic acidpropylene glycol polymers, isophthalic acidethylene glycol polymers, fumaric acidpropylene glycolbisphenol A polymers, and terpene-maleic anhydride polymers,

g) polyamide resins selected from the group consisting of: dirnerized linoleic acidalkylene diamine polymers, polycaprolactam, and sebacic acid-hexamethylene diamine/caprolactam polymers,

(h) polyamine resins selected from the group consisting of dimerized linoleic acid-poly- (alkylene amine) resins with free amino groups, polymethyl ethyleneimine, polydimethylaminoethyl methacrylate, poly N- vinyl carbazole, and poly N-butyl vinyl quinoline,

said synergistic combination being fusible with said polyolefin at processing temperatures up to 350 C.

2. The composition of claim 1 wherein the synergistic combination consists essentially of 95 to 99% by weight of poly N-vinyl methyl oxazolidinone in combination with l to 5% by weight of polyvinyl alkyl ether.

3. The composition of claim 1 wherein the synergistic combination consists essentially of 95 to 99% by weight of poly N-vinyl pyrrolidone in combination with 1 to 5% by weight of a polyester condensation resin.

4. The composition of claim 1 wherein the hydrophillic polymer is 25 to 70% by weight N-vinyl pyrrolidone and 75 to 30% by weight vinyl acetate and said secondary additive is a polyamine resin.

5. The composition of claim 1 wherein the hydrophillic polymer is 50% by weight N-vinyl methyl oxazolidinone and 50% by weight vinyl acetate and said secondary additive is partially hydrolysed polyvinyl acetate with 20 to 70% by weight of residual acetyl groups.

6. The composition of claim 1 wherein the hydrophillic polymer is 50% by weight N-vinyl morpholinone and 5 0% by weight methyl methacrylate and said secondary additive is a polyamide resin.

7. A polymeric composition having improved affinity for dyes consisting essentially of a hydrophobic stereoregular polyhydrocarbon selected from the group consisting of polypropylene, polystyrene, poly-4-methyl-1-hexene,

and polymethylbutene, said polyhydrocarbon having concentrated in the amorphous regions thereof 1 to 20% by Weight of a synergistic combination consisting essentially of 95 to 99% by weight of a hydrophilic, non-soluble polymer at least 25% of which is derived from an oxygen containing N-alkenyl heterocyclic monomer, and correspondingly 1-5 by weight of a secondary polar polymer, said polar polymer being selected from the group consisting of:

(a) polyvinyl alkylethers selected from the group consisting of: polyvinyl ethylether, polyvinyl methylether, and poly(viny1 methyl ether/maleic anhydride),

(b) polyvinyl esters selected from the group consisting of: polyvinyl acetate, polymethyl methacrylate, polybutyl methacrylate, and polyethyl acrylate,

(c) poly acids selected from the group consisting of: polyacrylic acid, polymethacrylic acid, sulphonated polyvinyl toluene, poly(ethylene/ sodium styrene sulphonate), poly(styrene/maleic acid) partial esters, and poly(ethylene/maleic acid),

(d) polyhydroxy compounds selected from the group consisting of: polyvinyl alcohol, partially hydrolyzed polyvinyl acetate with 20 to residual acetyl groups, and hydroxyethyl cellulose,

(e) epoxy polymers selected from the group consisting of: bisphenol A-epichlorohydrin polymers with no reactive epoxy groups, and bisphenol A-epichlorohydrin polymers with reactive epoxy groups,

(f) polyester condensation resins selected from the group consisting of: adipic acid-propylene glycol polymers, isophthalic acid-ethylene glycol polymers, fumaric acid-propylene glycolbisphenol A polymers, and terpene-maleic anhydride polymers,

(g) polyamide resins selected from the group consisting of: dimerized linoleic acid-alkylene diamine polymers, polycaprolactam, and sebacic acid-hexamethylene diamine/caprolactam polymers,

(h) polyamine resins selected from the group consisting of: dimerized linoleic acid-poly(alkylene amine) resins with free amino groups, polymethyl ethyleneimine, polydimethylaminoethyl rnethacrylate, poly N-vinyl carbazole, and poly N-butyl vinyl quinoline.

said synergistic polymer combination being fusible with the polyhydrocarbon at processing temperatures up to about 350 C.

References Cited UNITED STATES PATENTS 3,003,845 10/1961 Ehlers 260895 3,098,697 7/1963 Cappuccio et al. 260897 3,312,755 4/1967 Cappuccio et al 260 897 3,137,989 6/l964 Fior et al 57140 3,151,928 10/ 1964 Cappuccio et al a- 260895 3,256,364 6/1966 Bryant et al. 260895 3,361,843 1/ 1968 Miller et al 260895 FOREIGN PATENTS 834,160 5 1960 Great Britain. 916,244 1/1963 Great Britain.

218,828 11/1957 Australia.

MURRAY TILLMAN, Primary Examiner M. J. TULLY, Assistant Examiner US. 01. X.R. 

